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KARL scHmMAoHER. KARL zAHN; ERWiN-HCFFA, AND HANSTHE NA, or nocns'r- Patented 3,

' ,omTHE- AIN, GERMANY, ASSIGNORS, BY-MESNE assrem nnrs; 'ro GENERAL, ANILINE won zs, me, or NEW YORK, it. Y a CORPORATION on DELA RE sunsrrrurnn THIoINnIeo VAT nynsrnrrsiiiinrnocnss F'M KI'NG THEsA rE The present invention relates. to the new asyminetrical vat dyestuffs ofthe thioindi goid series being substituted by atleast one 5 alkoxy group. i i

More particularly: our inventionis concerned with the dyestufls of the folloiving general formula wherein X and Y re resent h dro 'en or an substituent, at least one Y being a- -substitu- 'ent, the constitution being such that the left hand side of the formula is not identicalwith the right-hand side of the'formula. The said:

dyestufis are in a dry state red powders, in soluble in water, alcoholand ether; soluble in nitrobenzene w th a redcolor, soluble n c concentratedsuliuric acid Witha green color, forming with an alkaline hydrosulfite solution yellow, vats, from whlch animal and vegetable fibers are dyed red shades; which are fast to light; chlorine and Washing.

tutedzketothionaphthenes, the corresponding sponding arylthioglycoliccarboxylic acids or acylketotliionaphthenes obtainable from the said acids by condensation with acetic anhyw 45 .dride, to'reactibn with thel-aniles of 'substi tuted diketodihydrothionaphthenes.

'preachingthat'o'faliuarine. A a 1 i (3) 243 parts of '3-i'nethyl-5;br0n 0'-2 ket0- rm Drawing. I Application "m d August 1, 1924,56ria1-No. 729,'ee7,- and m-eermany September 17, 1923.

lhe great valueof thes'e'dyestuffs resides in a the fact that their shades approach that of the" alisiarine and th'atthey possess'excellent prop {The following examples illustrate our'inv venti onz v e (1.). 194' parts'of 5-ethoxy 2 ketothionaphv thene (likewise known .as 6-ethoxy-3 oxyel V l-thionaphthene) are dissolved 5114000 parts" 1 ct glacial'aceticfacid and "there arggjaddv Led 330 parts of3methyl 5-chlor0-12 dihydro 2 ketothionaphthene- 1 A p-dimethylamino anile (likewise known as 4c Iriethyl-6-chlo're- 2.3 dihydro-3-keto-l thionaphthene 2- ('p-di- 3 r niethylamino)'-anile) .Whichcan. be: prepared by acting with nitrosodimethylaminileupon 1 7 an alkaline solution of the 3-methyle5-chloro Q-ketOthionaphth'ene. Y This mixture is heated for some tinie until: the separation of the new dyest'ufi iscomplete; The dyestuff separated V by'filtrationrforins, iwhen dry, a red crystal 7 powderjwhen' mixed With alkalineihy drosulhte t gives easllyfa vat Wh1le forming a yellow solution' It; dyescotton'a, fast clear Our new dyestufis are obtainable either-by Shme subjecting'the l-aniles of such diketodihydro-rr thionaphthenes as contain an allryloxy group inJ neta positionzto the sulfur atom and also H their further substitution products substi a tuted in the nucleusyto reaotionwith substi 7 The same result canbel obtai-nedby using instead of 3 rnethyl 5-chloro-2 lretothionaph thence.

; l f forftheianile used; in hlzsainple 1:1 are substituted 375,- parts 3 of 3-1neth'yl-5-' brolno e dihydro-2 ketothionaphthene-l (p-diniethylainino) -anile obtained iofi a somewhat bluer shade a V l (obtainable like the ehloro-c'ol'npound) a similar dye'stufl 1st thionaphthene are dissolved in 2000 parts of nitrohenzene and 200 parts of glacial acetic acid, there are then added 326 parts of -ethoxy-1.2-dih dro2 ketothionaphthene-1- (p-dimethylamino)anile and the mass is heated to 80-100 C. until the formation of the dyestuif ceases. After cooling, that dyestuff is filtered off and washed. It is identical with the product obtained according to Example 2. a

(4) 228,5 parts of l bromo-5-ethoXy-2- ketothionaphthene are subjected to reaction as indicated in Example 1 with 330 partsof the anile mentioned there. The resulting red dyestuil' dyes cotton from the vat loluer shades than that-obtained according to Example 1.

(5) 326 parts of 5-ethoXy-1.2-dihydro-2-. lzetothionaphthene 1 s (p dimethylamino) anile are gradually heated to boiling with 233 parts of 3-methyl-4l.5d1chloro-2-ketothionaphthene and 4000 parts of glacial acetic acid. The formation of the dyestufl is com-j plete after some time. The product is filtered, washed with' glacia l acetic acid and ton a red shade with a blue hue.

dried. The dyestufi thuscbtained dyes cotl (6) By. substituting for tl18 56tl1OXy2- V ketothionaphthene as used in'Example' (2) 182 parts I of; 5 methoxy-2-lzetodihydrothionaphthene 'ared dyestuli is obtainediwhich dyes cotton a: red shadewith a blue hue (7) 256 parts of 4-ethoXyphenyl-2-th1oglycol-l-carboxylic acid. are heated to boiling parts of" 3-methyl5 chloro1.2 dihydro-2-ketothionaphthene 1 L (p-dimethylamino)-anile and about 2000' parts of with 330- acetic anhydridei- After a short time, the dyestuff begins to separate. Thelmass is then heated until the formation of the dyestuif ceases. The dyestufl obtained dyes from the vat cottona shade resembling alizarine'. I

(8) If for the anile used in examplefi) are substituted 375 parts of 3-methyl 5-bromo 1.2-dihydro' 2 ketothionaphthene 1 p-dimethylamino) anile and the further operations are carried out as indicated in this example, a dyestuif'of' a somewhat bluer shade is obtained;

i (9)" If for'tlie 256 parts of l-ethoxyphenylj Example The dy'e'stuff thusobtained is identical with that obtained according to EX- ample 11) If for the 2000 parts ofacetic anhydride as used in Example (7 are substituted 1500 parts of nitrobenzene and 500 parts of acetic anhy dride and the further operations carried out as indicated in this example, a dyestuff of the sameproperties is obtained.

The properties of the vat dyes produced according to this invention may in general be characterized as follows; .In the form of a dry powder they are of a red color. They are insoluble in water, alcohol and ether. They dissolve in nitrobenzene with the formation of red solution and in concentrated sulphuric acid with the formation of greensolution. They dissolve readily in alkaline hydrosullite solutions forming yellow vats from which animal and vegetablefibers are dyed red shades.- The dyes produced possess excellent fastness to light, chlorine, washing, alkalies and acids.

Throughout the specification the numbering recommended by chemical abstracts has been used in designating the chemicalr compounds used or prepared in the processes described herein. 1 Having now described our invention what we claim is:

1. Asnewproducts, the herein described asymmetrical vat dyestuffs of the thioindigo series having most probably the following formula:

wherein X and Y'represent hydrogen or. any

substitutent, at least one Ybeing a substitut-v ent, the; constitution being such that the left-handside'of'the formula is notidentical 'with' the right-hand side of the formula,

which d estufis are in a dr 7 state red owders insolublein water, alcohol and ether, soluble 'in nitrobenzene with a red color soluble in concentrated sulfuric acid with a green color, forming with an alkahne hydrosulfite solu- 171011 yellow vats, from'which animal and-Vega table fibers; are dyed red shadesfvv'hich are" fast tolight', chlorine and washing.

2 As new products, the indigoid dyestulfs I of the formula'i in which 'X stands for halogen, beingin a drystate red powders, insoluble in Water,-

alcohol and ether, soluble in nitrobenzene of the formula:

light, chlorine and washing; c

5'. As a new product, the'herein described 7 I with a red color, solubleinconcentrated sulfuric acid'with a green color, forming with an alkaline hydrosulfite solution yellow-vats, from which animal and vegetablefibers are dyed red shades which are fast to light,

chlorine and washing.

3. As-new products, the indigoid dyestuffs i CH3 in which stands for a halogen, being in a f dry state red powders, insoluble in water, alcohol and ether, soluble in nitrobenzene with a red color, soluble in concentrated sulfuric acid with a greencolor, forming with an alkaline hydrosulfite solution yellow vats, from which animal and vegetable fibers are dyed red shades which are fast to light, chlorine and'washing,

4. As new products, the'herein described vat dyestuffs of the'thioindigo series, having most probablyv he following general structural formula: f .c

being in a dry state red powders, insoluble in water, alcohol and ether, soluble in'jnitrobenzene with, red-color, soluble in concentrated sulfuric acid with agreen color, forr n ing with an alkaline hydrosulfite' solution yellow vats, from which animal and vegetable 1 fibers aredyed red shades which are fastlto vat dyestuffs of the thioindigo series having the following structural formula-:

derived by the condensation of a l-anile of 3 methyl 5-chlor} 12- diketo dihydro thio naphthene with 5-etho2iy-2-keto-thionaphprobabl Q :thefollowin general structural .f 1 y, I c a ..ormu a; l w

i f Loo wherein 3 indicates an arylwgiroup, conta'ining'as a s'ubstituent angalkyl-oxy group,b eing in a dry'state'red powders, insoluble in water, alcohol; and ether, soluble in nitro benzene with a red colonsoluble in concentrated sulfuric acidflwithagreen color, forin- 7 ing with an alkaline hydrosulfite solution yellow vats, from which animal and vegetable fibers are dyed red shades, which are fast to light, chlorine and washing. 7

7. As new products, the indigoid dyestuffs? I ,of the following'formula wherein: X hydrogen or halogen i and X'stands for'halo'gen being in'adry state red powders insoluble in water, alcohol and ether, soluble in 'nitrobenzene with a redgcolor,v soluble in concentratedsulfunc acld wlth'a green color, forming withfan alkaline hydro- A sulfite solution yellow vats, from which animal and vegetable fibers are dyed red shades which are fasttolight, chlorine and washing.

. 8. As new products,;the indigoid dyestuffs of the following formula:

wherein Z stands for; methylor ethyl being in a dry'state redpowders insoluble in water,

lilo x alcohol and'ether, soluble in "nitrobenzene witha red color, soluble in concentrated sulfuric acid with a green color, forming with an alkaline hydrosulfite solution yellow vats,

from which" animal and. vegetable fibers are dyed red shades whichiare' fast w light, U

chlorine'and washing. 7

9. As a new product, the herein described thioindigo vat dyeof the following probable structural formula V 'CHa 9 l Br of 3-Inethyl- 5-chloro:1.Q-diketo-dihydro-thi'o napthene with a broino 5 -ethoxy-2-keto-thioo which isobtainableb'y condensing a l-aniles naphthene; being in aclry state-albriglit re'cl 1 p0wder, insoluble in water, alcohol and ether, soluble in nitrobenzene with a bluislv red color, soluble in concentrated sulfunc ture's.

bright bluishred shades acid with a green color, forming with an alkaline hydrosu'lfite' solution a yellow vat from which animal and vegetable fibers are dyed fast to light, chlorine'and Washing. v

In testimony whereof, we aifix our signal-- KARL SCHIR-MACHER;

' KARL 'ZAHN;

ERWIN HOFFA. HANS HEYNA. 

